LOSSES  OF  MERCURY  IN  TOXICO- 
LOGICAL ANALYSES 


BY 


KENYON  A.  HYLE 


THESIS 

FOR  THE 

JJEGREE  OF  BACHELOR  OF  SCIENCE 

IN 

CHEMISTRY 


college:  OE’  libeijal  arts  and  sciences 


UNIVERSITY  OF  ILLINOIS 


1922 


(a.  Co' 


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TABLE  OF  CONTENTS 


Acknowledgement  Page 

I  Introduction  1-4 

1.  Purpose  1 

2.  Nature  of  the  prolblem  1 

3.  Historical  1-4 

II  Experinsental  4-12 

1.  Material  4 

2.  Preparation  of  Material  4-3 

3 . Fresenius-Von  Baho  Method  5-8 

4.  Chit  tendon  and  Donaldson  Metiiod  8-9 

5. Hal?kins  and  Swain  Method  9-10 

6.  New  Methods  tried  10-12 

III  Results  and  Discussion  13-17 

IV  Summary  and  Conclusions  18 

V  Bibliography  19 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/detaiis/lossesofmercuryiOOhyle 


ACKNOWLEDGEMENT 

I take  this  opportunity  to  thank  Dr. Beal  for  the 
suggestion  of  this  problem, and  for  his  S3mipathetic  sup- 
ervision and  guidance  in  working  it  out.  His  friendly 
suggestions  and  personal  interest  have  been  a source  of 
inspiration  to  me  throughout  the  work, and  if  anything 
of  importance  has  been  brought  out  in  this  work, it  is 
largely  due  to  the  above  facts. 


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(1) 


LOSSES  OF  MERCURY  IN  TOXICOLOGICAL  A^I/lLYSES 
I. INTRODUCTION 

1 . -PURPOSE 

The  purpose  of  this  investigation  has  been  the  study  and 
comparison  of  the  three  principal  methods  for  the  decomposition 
of  organic  tissues  in  the  toxicological  determination  of  mercury, 
in  order  to  determine  which  of  the  various  methods  no\f  kno^m  and 
used, will  recover  the  grea,test  amount  of  mercury  from  organic 
tissue . 

2.1S.TURE  OF  THE  PROBLEM 

It  is  a well  known  fact  that  mercury  salts  together  with  other 
salts, such  as  arsenic, are  quite  volatile, and  it  is  due  partly  to 
this  fact  that  no  method  is  now  l-:no\m  wliich  will  recover  all  of  a 
given  quantity  of  m.ercury  in  a toxicological  analysis.  It  is  very 
important  inaa  toxicological  investigation  to  know  the  exact  quan- 
tity of  mercuhy  which  has  been  administered  to  cause  the  death  of  ' 
the  person  in  question.  Proof  that  a sufficient  quantity  of  poison 
has  been  given  to  cause  death  constitutes  the  chief  evidence  in 
legal  cases.  Therefore  it  is  necessary, in  toxicological  analyses, 
to  Imow  how  much  mercury  is  lost  in  the  composition  of  the  organic 
matter  and  the  subsequent  determination  of  the  poison. 

3. -HISTORICAL 

The  methods  used  for  the  toxicological  determination  of  mercury 
are  comparatively  few  in  number.  The  chief  object  in  all  of  the 
methods  is  the  complete  destruction  of  the  organic  material.  This 


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is  necessary  in  order  to  free  the  mercury  from  organic  substances, 
chiefly  the  albuminoids.  Mercury  forms  a complex  salt  with  albumin- 
ous substances  present  in  protein  material , and  this  must  be  broken 

before  the  mercury  will  go  into  solution. 

(8) 

I. ldlESENIUS&  VON  BABO  MET^IOD 

Fresenius  and  von  Babo  worked  out  a method  for  the  determin- 
ation of  arsenic  which  was  published  in  1844.  This  has  been  adapted 
for  the  toxicological  analysis  of  all  metallic  poisons  including 
mercury.  In  this  metnod  the  decomposition  is  carried  out  by  the 
action  of  nascent  chlorine  upon  the  organic  tissue.  The  chlorine 
is  generated  by  the  action  of  hydrochloric  acid  on  potassium  chlor- 
ate,both  of  wiiich  are  added  directly  to  the  tissue, which  has  been 
chopped  finely  and  diluted  with  a little  water.  The  reaction  takes 
place  best  when  heated  at  the  temperature  of  the  steam  bath.  The 
decomposition  requires  several  hours.  The  liquid  is  filtered  off 
and  the  mercury  precipitated  with  hydrogen  sulphide.  The  mercury 

may  then  be  determined  by  any  suitable  method. 

(1)  / 

II.  GAUTIERS  METHOD 

Gautier  worked  out  a method  for  the  toxicological  determination 
of  arsenic  which  was  published  in  1875.  This  method  of  decomposition 
consists  of  oxidizing  the  material  with  concentrated  nitric  and 
sulphuric  acid  at  rather  high  temperatures.  To  100  grams  of  the  mat- 
erial 30-60  grams  of  pure  nitric  acid  is  added.  Then  one  gram  of 
sulphuric  acid  is  put  in  and  the  mixture  heated  until  liquif ication 
is  produced.  It  is  then  removed  from  the  heat  and  8-10  grams  of 
sulphuric  acid  added.  This  is  then  heated  again  (taking  care  not 
to  carbonize  the  mass)and  taken  from  the  source  of  heat.  Nitric 
acid  is  then  poured  over  the  material  a little  at  a time  until  up 


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on  heating  to  a point  where  dense  white  vapors  come  off, there  is 
left  in  the  casserole  a hrovrn  thick  liquid  carhonizahle  at  the  boil- 
ing temperature  of  sulphuric  acid.  V/hen  the  nitric  acid  produces 
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(2)  (3) 

Orfila^s  proceedure , published  in  1853, and  i<ilhol’s  w^ork  published 

in  1848. 

(4) 

III.CHITTENDBN  & DONALDSON  METHOD. 

Chittenden  and  Donaldson  while  endeavoring  to  find  a more 
suitable  and  accurate  method  for  the  toxicological  determination 
of  arsenic , worked  out  a modification  of  uautier's  proceedure , which 
was  published  in  1880. They  claim  its  advantage  over  the  method  of 
(lautier  because  the  decomposition  is  carried  out  at  lower  tempera- 
tures. In  this  proceedure  the  sulphuric  acid  is  not  added  until 
the  nitric  acid  has  practically  reduced  the  organic  material  to  a 
liquid.  This  liquid  is  then  watched  closely, and  when  it  becomes 
thick  and  assumes  an  orange  shade, the  casserole  is  taken  from  the 
hot  plate  and  3 c.c.of  concentrated  sulphuric  acid  added  while  stirr 
ing  constantly.  The  addition  of  the  sulijhuric  acid  to  this  residue 
rich  in  nitrous  comjx)unds  causes  nitrous  fumes  to  be  given  off  co- 
piously, follovt'ed  by  dense  white  fumes.  The  residue  is  carbonized 
to  a black  sticky  mass  or  else  a dry  char.  After  heating  some  more 
and  adding  a few  c.c,  of  nitric  acid, in  order  to  more  completely 
destroy  the  organic  material, and  prevent  formation  of  sulphided, 
the  casserole  is  removed  from  the  heat.  A hard  carbonaceous  mass 
free  from  nitric  acid  is  the  result.  The  arsenic  may  then  be  dis- 


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solved  out  with  successive  portions  of  warm  watoi'jand  determined  as 

in  the  previous  method.  ^ ^ 

(§) 

IV. HARKINS  AND  SWAIN  iH^THOD. 

Just  as  the  Chittenden  and  Donaldson  method  is  a modifica- 

(l) 

tion  of  Gautier’s  so  may  Harkins’s  and  Swain’s  proceedure  he  call- 
ed a modified  chittendgn-Donaldson  method.  The  proceedure  differs 
from  chittendon  - Donalds()n^ method  in  that  the  mixture  is  the  cass- 
erole is  removed  from  the  heat  just  as  soon  as  it  htis  ’been  complete- 
ly reduced  to  a liquid.  After  codling  the  liquid, about  30c. c. of  cnn- 
centrated  sulphuric  acid  is  added  and  the  casserole  heated.  Great 
quantities  of  nitrous  fuires  are  driven  off.  Y.'hen  the  liquid  begins 
to  get  bro^m, nitric  acid  is  added  from  a dropping  funnel, in  suff- 
icient quantity  to  maintain  the  brown  color, and  prevent  any  further 
darkening.  This  is  kept  up  until  the  liquid  in  the  vessel  no  longer 
changes  color.  This  thick  liquid  is  now  free  from  nitric  acid  and 
a great  deal  of  sulphuric  acid  is  also  gone.  It  is  diluted  and  evap- 
orated to  a smaller  volume  and  is  then  ready  for  the  precipitation 
of  mercury. 

All  of  the  above  methods  were  used  by  the  authors  for  de- 
tertiination  of  arsenic, but  have  since  been  adapted  for  mercury 
and  other  metallic  poisons. 

II .EXPERIMENTAL 

1 . -MATERIAL 


The  material  used  in  this  work  was  dried  blood.  This 
dried  blood  was  of  very  low  moisture  content, so  that  twenty  five 
grams  of  the  dried  material  was  taken  to  equal  one  hundred  grams 
of  tissue.  In  all  determinations  this  amount  was  used. 

2. PREPARATION  OF  MATERIAL 

The  dried  blood  after  being  weighed  out  roughly, was  put 


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V*^'  '.<<u'^r*r^i0H-  ?;iU‘ '■ 

«->■'.  -r?  • .V  . ;•■ 

■ 0(%  t?>*t**v  ^4:  <T7tJ^vif7‘^;5  4t(tT 

‘ I ■ ,.r  .'*'•■  "^  *.  ■' fv--  ■'■ 

^ b^^i^  .’>J'|- fn^o;i»  ; ( V'-jI  g.  .i  Aii'tiil  '<ai  ff;?  aXIitf 


'I  ^ J ^ '^*"  .'=.■■1 


:-^  > J' 


•ia 


*7,<%  *-' 


’ .-Mm 


i’\-  >' 


t 

VJ- 

> J*uff  i CK* 

f."'  ^ 

.r*'  -.Hi  !ft-fC>l*Xu«  ^If  yv<)ch.  '3/-  '■  H 


T t 4 


I 


J * V/JU ?»'(/%  i *l4i’i 


♦a  k • > 


'J  li'Jofll  i^4^i  ‘V.>d  Kfijo  , 

’ , ■ . *,*^  , '•  ' t * * ?■'  ^ 

^ I ' ' .'  ■ , '“‘  ' ^ . V''  ■.,-'I|» 

ryno.ftIo*T  oil? ft.  • 


i9 


. 1 


■^'  % 


a/*v«a  . '1 


.vXX 


I ..  I 

' r 


A *. 


. *’»•  »!%■*'  * , 4 •»  I 


,;  V r -Pr^  ■ _ 

i(rro|r 


.'  f i I'xifii'.  io.ft  Ttoi  c '*>v  io  •(tii  .^oolrf 


'.r  T • o«rt»<fVtfli*l  i*dX**4i  9ffc®to 

.■■■  ■*  * ' ■ '1 

' . ‘ ‘^7  ' ’ *4'J 

.'lif  fcUMvUi  0i4i  ir^^Ot'XWlf '-‘t'>  •‘•i£»  tX*' u4  ; • W 6 ti  'lu 


ipir  o».*»,Tta,  ui '{  im  iM’OiiX  JK‘|M»'iiflv 

ij 


(5) 

into  "S'  veS5'el”'n:iT(r'^STnr^li  W£lt0f~  i.dded  to  form  a pasty  or  soupy  mass  . 
This  was  then  allowed  to  stand, in  general , about  an  hour  in  order 
that  the  blood  might  become  softened  and  brought  to  a state  as 
nearly  resembling  the  original  condition  as  possible. 

Mercuric  chloride  was  chosen  as  the  most  suitable  mercury 
compound, since  it  is  the  most  common  of  the  mercury  poisons  to  be 
dealt  with  in  toxicological  work.  By  adding  the  mercuric  chloride 
to  the  blood  mixture  in  the  form  of  a solution  in  all  cases  we  felt 
that  we  had  a fair  duplication  of  toxicological  conditions.  This 
solution  was  of  Imown  titer, and  was  retitrated  frequently  to  detect 
any  change  in  strength  which  might  take  place  from  time  to  time. 

The  solution  was  made  up  of  approximately  tenth  normal  strength, in 
order  to  facilitate  the  addition  of  mercury  in  small  amounts  to 
the  material. 

After  adding  the  mercuric  chloride  to  the  material , the 
blood  mixture  was  allowed  to  stand  forty  eight  hours.  This  gave 
opportunity  for  the  mercury  to  thoroughly  impregnate  the  organic 
matter, and  reach  a condition  somewhat  similar  to  that  existing  in 
the  animal  body, when  death  and  possibly  burial  follows  adciinistra- 
tion  of  the  poison.  It  is  supposed  that  mercury  forms  a mercury 
albuminoid  in  the  tissue.  It  is  due  to  this  fact  that  organic  m.at- 
erial  must  be  destroyed  before  mercury  can  be  determined.  After 
standing  this  length  of  time  the  decomposition  may  be  started  accord 
ing  to  the  method  selected. 
l.-WORK  ON  THE  FRESENIUS-VON  BAB^fliETHOD. 

In  carrying  out  the  decomposition  by  this  method  it  was  de- 
cided to  vary  the  proceedure.  One  set  of  decompositions  was  carried 
out  in  an  open  flask, and  another  set  using  a reflux  condenser.  By 
using  the  condenser , any  mercury  which  might  volatilize  with  steam 
would  be  returned  to  the  flask  and  thus  be  determined.  By  comparing  < 


ivtSt 


T2 


'M-W  ’r’VfT 

H .t  fif-  'rt>  oi  ^^oj;i»iw»?«.  i?»a'”’BJtffr  jj 

. ^ , ' • " ■•  '’  . 'I  t 

«/>  9Jh’ vti^  0 Oi!*  l,*^’!!4i<*^'^Ci  l'«ij-  J*'‘  r>.nOOO^  U.'  * ' iuif.)  I) 


- ^ ^ .1 

. , «aXJiIiaA,i  tcfU.^i’Ta  f»<it  ^l'x**an  | 

^ ^ 'Shfhi  \^ilf  rr/j  abl*ioXif'r>  oln^o'r«l£.  5 


rt'Oi.*  ^*ui/>*i^r'  orft  1o  Uffga  . ) «iuvt  *)4.^  aJt  OdftI c'. , ftmiotrcoo 


;WjliCh/itt)  oilim'H*  I wt^  . -rrX  ft.t  NT^Xitt{U>  Q 


t * 1 

rsM  fnf  j ti«  ff»  unljnjf^a.u  Hto'f  o**it  fT^'Q-UiJxta  hooiff  ttf 

■-  - ■*  }%■ 
1. . •■  ' »-  . .1  (j 

. ^^liT  .3a, are  moil  To  ® fw»xC  ‘j4! 


5 rt#  y C.tll'D'lpft'1'l  Ji,*J  tWi.  ffworttf  *4o 


i^OlOH  jii 
Xttf 


3 . • , M ’ • ''T-  ■ 

ytt^i.**  f ^0  iw  aflW^al^ulopi  6Jfi^ 

‘ ' ' ' • ' " ' " ;-  ' ’'‘M  ' ..  ^ ■ 


nf  tiK’.a  «4  'o  944>4XX-Xo«l  oJ  *iQh^o 


mts,: 


¥ 


i?>.\;‘-  'f  , K ■'  -•  -'.i  . 

0«C;»  oA'ii»c*»f^a  j.  - 

* ^y»i;  aTif*  ,^4ti;orf  ^4'fo'5  oi  hov<il  ltA  fliiiiixlift  ^olo 

. ^ ' . ' ' ‘h’'' 

T>hrH^’*o  <ic14  oX wrir* Mj  od4  y.i'XvijqJ'Soq^o 

itl!  fi‘i i^.ii  i*t  »t  rtoiiot  ,ij?ia,t5vi'^/v4i 

% * “ 


«3*tJ  vtai  u’ « a '(^oXlIo?  In I'Kivf  o>'(w,^!^d  C/wttnifc  dfU 

' ^ 4.  f -tqqquB  «di  .s^oeXoq  nift  lo  huJ^^ 

\ foiJX  4 «i:Xf  nui;  Ht  vTI.  . jX  i^Xo'iteicrXii) 


a'*4’»K  .^nfl|:h«^:>40ii  tuX  irr.*!  o ?Cl  j«E  Jbov.oxiaob  9d  i«ur*i  JIaXio 

•i(Jor>A  nrf  itoi.iire*i!tjitfou^l>  o4^  5flLtbno4^B  & 


'*'*  * ♦ 

, .S»^v0l»e  hnJ^ottt  aifi  od  aftfc  ^ 

^ .‘uo'.isi^liua  wiT-sux'mHirt  ait#:>;o  x*'\-.x  S 


-{»b  uiy7>*  &0lirv-'(  fliitt  JioirJlfio  • r>fi,r)  »#tt  ,ruo  »/(rXy*i*tBa/qrX'^ 

.^'‘f»»>J:‘X*ir  r *?4f  (?nr‘*'\^i^'9»oif..r.'')oJb  'Xb  sdJ'  o4  i>»l»iid^; 


■'.» 


'C  .*10/ iiijXiM'iff  Kf.^£'t^>•I  A jMrJb^u  ‘i^rorrn  r f?4i,rfaaIT  a'?«!:o  rt>i  «t.  jup 

jI4;N  o»£UJj)lnv  tn^^^tiu  rt7hi4w  'C^tioioM  r.ast'thMoPnQd  i>tlj^  j\fxXtiu 

f '' 

nn-vmo  a «ud4  X»nn  afe&Il  arfX  odl  f.O(tanin*T  &d 

•~:^iCTr^:fe^in«Mr  '-'mwarMii  apMtf..':/  r , 


i.  vl 


(6) 


the  results  of  zne  two“airrerentiy““c6riauctea  clecorfiposltlons , the 
amount  of  mercury  lost  hy  volatilization  might  be  easily  found. 

Following  the  proceedure  of  Fresenius-Von  Babo  thirty 
c.c.  of  concentrated  hydrochloric  acid  was  added  to  the  mixture 
followed  by  from  one  to  two  grams  of  potassium  chlorate.  The  Kjel- 
dahl  flask  containing  this  mexture  was  then  put  on  the  water  bath. 

The  nascent  chlorine  coming  into  contact  with  the  organic  material 
soon  began  to  act.  After  a short  time, when  the  potassium  chlorate 
was  used  up, more  was  gradually  added(about  .2  to  .3  gram  at  a time). 
Generally , this  amount  added  about  every  five  to  ten  minnutes  kept 
an  even  flow  of  chlorine.  The  mixture  soon  began  to  get  lighter  in 
color.  Shaking  the  flask  after  addition  of  each  portion  of  potass- 
ium chlorate  accelerated  the  decomposition  noticeably, by  bringing 
the  chlorine  into  contact  with  the  tissue.  The  end  of  the  decompo- 
sition was  indicated  when  the  liquid  assumed  a light  straw  color, 
and  did  not  darken  on  standing, or  upon  further  heating.  A little 
dilute  sulphuric  acid  was  then  added  to  precipitate  any  possible 
barium  or  lead  and  the  supernatant  liquid  was  filtered  off.  The 
mercury  was  precipitated  from  the  solution  with  hydrogen  sulphide, 
after  expelling  all  free  chlorine.  The  gas  was  allowed  to  buble 
through  the  liquid  for  one  and  one  half  hours  while  hot.  The  liquid 
was  then  removed  from  the  water  bath  and  the  gas  allowed  to  run  tin- 
til  the  flask  cooled.  The  liquid  containing  the  mercury  sulphide 
precipitate  was  ccrke^iL  and  allowed  to  stand  for  one  day.  If  at  the 
end  of  that  time  an  odor  of  hydrogen  sulphide  was  noticeable  in  the 
flask, the  precipitate  was  filtered  off.  Otherwise , more  hydrogen 
sulphide  was  passed  into  the  liquid.  The  black  residue  of  mercury 
sulphides  was  then  dissolved  in  nitric  acid  with  a few  drops  of 
hydrochloric  acid  and  the  resulting  solution  diluted  and  filtered. 

This  filtrate  containing  the  mercury  was  then  ready  for  determinatio:  >. 


! 


^Tiar);*ir»  ■/ 1 '^r'r^V’  i ^ i f ^ - od«if y..-  ■ 'lit 


• « ' , 'ij« 


flit 


^ ^ ^ ( tj* 

<.  'iaroNli<'f  y;' > 4<»fl^to.V  7^'Vfi , » 


li  . 


'I* 

^ -A*llX%'ri  . j!U?(.*'«y4j  \i|  mr^  ni  *<!•.,  yrf 

♦ P fto  vWf.|  .i4'»'  e'^;.vfiL#H«  Kft!^ 

l*  -^  , \ ■:•  ? . ,v  ^ S!*'  - 

I^Jb'f'*-?:#i/f.  ?N^^VW  /5«i4  * li.  tlu-jjj.g>a^^^  ?^r»liat>^  OrtJF<^otXrf^v|it!^o^r! 

<niifi  <;  4' r-  b'\.i  iiJj'ii*',/t’j(ljil^  M h&^HIa  ^»3ia  oi  tu^ino'i  pnp0e 

{ ■'','  ■ .,  ' > '!  ' , - 

i J«<  C.  uJ  Vr  viifvp -X 1 I1#uCm^  4«^  ^noa,(j;>r  ftoo-u  aiiv 

• ' *i'L  v/>»v>  ^ Jy.^h.'  4>rUK»lir>i  ^trTj 

Jft  i 1 iwj  '4.f  (Wo2«  f>t;i  a**  iSttVe 

._  ' lO  '■  ■ . • '.■.  . j;;>- 


!-yj 


f 


•r-j 


-n 


iX  '...,-  ' Vj  ■ j: 

^ ,n>-CtV*7  Wi<*f-» ; w*>$ f ■ ' ‘ t'xi/jrfji,  <>((  •t^H'ic  ji'iiTT 

' • *>  - 4 ■ “ ■ f'l  * 

' :a^:  '>.;■- 

'.‘;,4  7^--*  /i 

it*  V 

^>4**'  . i.'^n  /f)To*Xi’l  ftiir  4tAtjv-i4 


nil  jhfi  ,j  .,  "£j^f*v 

P ..  ' ■ i.  . _ ,1  I ■'-  • . ■ '<?»  A 

/tnTo^Xi’l  |tii»  wll  t>n«  iMtrtl  »fo  ftu/tfidtf 


, f ‘I'f  Ui>  U^r»A'ii  '^ij  i;VlW  tl^  »i<4  t7f>*tj^,liri.*ii*i,*  fr«t  X'S^nrwjJj 

».  ' T'“  " o *^*  ■ flt.'«  ■ -J  '*■ 


,,  (if  '■ir  ^ufle  mJI|»#  «wr',  ;il'^'.  fj'>ni  liirJiM.U  le>t; 

r* 

urW  .Ji  # n/fffi'  <»riu».  I livsiiiiiMju  lo'i  JbJu^yT  odrf 

»iti  ttt»a  oj  J 'Hrc'llo  lifss  <t»r!7  Bron'i  ij«iVq#?on 

- ■.  I fft  . < ■ '\  . •-  i </.•■ 

I»ffi  4^1lf-  V‘4tirvt<t*c3  ^ -j  t'XiiiftM  f»in  l4  i 


j0t  Ti.  . hf\a  JPM  e‘i^  iji^Mrjlppnq 


^ a 


li  "ycik  ii  ,/  'vr^ I u*»|ljffl^  *tyQ< 7MI  imtl  # oTrH'’ 'lo  %W 


r * 


**•  ^ ' ' ''‘'‘ii' 

y . t.-f  , >4.J  4<1V  otitit 

V*  fr  i;  *.  /U-t*'  hktH4  iJ9l|^ 

!j»onX»yft 


(7) 


The  determination  was  carried  out  volumetrically, using  the 
(5) 

method  of  Bauer .Following  his  proceedure  the  solution  was  made  alk- 
aline with  ammonia, and  a standard  solution  of  potassium  cyanide 
added  to  the  mercuric  solution.  Five  c.c.  of  potassium  iodide  was 
added  as  an  indicator  and  the  excess  of  potassium  cyanide  titrated 

with  standard  N silver  nitrate.  Each  c.c.  of  N silver  nitrate  is 
10  10 

equivalent  to  .02006  greims  of  mercury.  The  potassium  cyanide  solu- 
tion was  previously  titrated  against  the  N silver  nitrate  solution, 

10 

so  that  the  value  of  the  potassium  cyanide  solution  per  c.c.  was 
Imown . 

In  carrying  out  the  dujjlicate  decomposition  with  the  reflux 
condenser  the  potassium  chlorate  was  added  by  loosening  the  conden- 
ser from  the  flask  and  dropping  in  the  potassimn  chlorate.  It  was 
found  in  running  the  two  sets  of  decompositions  that  the  liquid  in 
the  flask  bearing  the  reflux  condenser  always  reached  the  final 
stage  before  the  open  flask.  Also, less  potassium  chlorate  and  acid 
were  necessary  than  with  the  open  flask, in  order  to  produce  the 
final  stage  of  decomposition.  No  difficulty  was  experienced  in  carry 
ing  out  the  decompositions  according  to  this  method.  However, some 
of  the  organic  matter  could  not  be  destroyed  by  the  action  of  the 
chlorine.  It  always  remained  in  the  bottom  of  the  flask  in  the  form 
of  a white  mealy  substance.  It  was  easily  filtered  off  , leaving  a 
clear  liquid.  The  most  important  source  of  error  seemed  to  be  in 
not  allowing  enough  time  for  complete  decomposition.  If  the  flask 
was  removed  before  it  had  reached  the  right  stage ,flifficulty  follow- 
in  precipitating  the  mercury  from  the  solution.  The  writer  experien- 
ced this  trouble  early  in  the  proceedure.  Stringy, slimy  compounds 
were  thrown  down  with  the  mercury  when  hydrogen  sulphide  was  passed 
into  the  solution.  These  were  later  dissolved  by  the  nitric  and  hy- 

il'  


' t *“• 


'Jr('. 


•‘Vf. 


sfosxxs^- 


‘Ti  ViV  i' 


I*  . 0iLtAi.V'  > ^<1  >^'H|,rJu^;5'!4;hfl/»j‘»“  » ic t* 

^ ■'  '•  1 ■■  ' , V-  ' 


1 


'fij:  m(rr‘'fCl  ilf 


■' '■  ■ •>>»*; -■  i’'>  ^ rf 

M>*v/  ’ » .a.t^  ov.W  ‘.•ioiv»#/t«>ii  6'j^ 


j4,  - '■  ' '“  I ‘ T*  '‘"ijiT 

‘ ftl  -a.r/)'Ta.»h  ').’P'i4i  "ir,  ‘ >w*vV-  H t>n<ibioKtl» : l^l'W 


#i  to^rl  ir  t 9tii  uni^iA  |.  >.r ♦v’# jC3  zmr 

L . a ;?/  .!>.y  7-.'^'nMj  alrlf^n  "»  w 1o  f>a|>:V  otidt  ^jHd‘  r*e 

n ■ V V , '•■  ■ ■;  ■ ': 


udW 

f:^  ' ■’  '-. 

,i*iU{'ii  ,/fv’)'>i.  ■vjiioti'w/itfiyVrrin  'v;r/io' ^/r  & 

' . .va  ,;'K; 


, » 'V  y.  " 1 

I*  ‘ ' ■t.,ivt^,n.)f».j  d.r#  ff)" 


K? 3 ■ • ■■  . • ■ ' _,-rn  <v- 


';.:tP> 


'*  T-i  ' " W ‘ ''  ■ ->  i'  ■i<-^’^:\-.  v ; 

|1  ^ ' *‘  . 

I Oil*  <a  4U tT'TNr^y^3?ii(vjtfi;i 

. >oi;  tacKfkMU^'V^  i<ua& 

li  ^ ' . ' -C  > ' V ■■''^■■^"in 

n >*a4J « ;t'ji  i o>r**b  • ^ris/U  ^(i  * 

B '\j  ft. i ;-.r*i ..  -ft5(4v4  ' &i '../»  > 'i<icrv 

^ . • • . . '■■/  ■ ' ■ ' ’.  ' '■^‘  , ® 
'>*fi  It*'  04f!' Ch<i/t.V/\r  .«t  4y4#rr  .^♦'d^ioXrt: 

■K'*  '■■IW'*" 

X*  i^v  X ,-i ’Ho?  t "^.'a-'rilit'iWJXt''  ^:^^^  ' 

'"■  * ait  'fiisT^ 

# '■*  ■ ■ - •)'  * > • ■■  , . ■ ^ . 

,,  ’iirf.*at  'i  t i *iki  .(Sffi'Ji  f ’ir-i  oiXvi 

*!  ■ ' y*^  , ■ ' ^ ^ ‘ 

- /X"  ’tl'ranti*,:-  -r,v.-iLi‘;  H.'J  f»4ttfuA0Tf 


2v-.;j(o  Ti§,i-;:'fy’  ' a.  .r 


• *1*  %•  ’#  »■  4 1 _ 

’lorn’  I 1.7  lUii]l*J  y%4<4'T50-^  d<ti 

. ?r;v  ■^■.  . • c 


f.f  .ruiD  mnb  f.tft  #.,  at 

i i.^A'  .(  'tj>v  ,i^>t'f'^la^’  iX‘>.>iVL(yc^f  kjoftir 

~ ' ‘ ^ * - ' » ' . “'I  4,  I 


i ^ f i*  ' 3.  wi 

ijt'h;  .»•  i,  fv  j ijj,  ^»)r /<■«•, «Jfc; 4 dioiia:tc 

> . .-'  » ,.“*  *#  ^V*v 

. ...  ‘ .<;u 


(8) 


drochloric  acids, with  the  result  that  when  the  anunonia  and  potassium 
iodide  were  added  for  titration, a murky  precipitate  clowded  the  sol- 
ution and  made  titration  impossible.  It  was  not  always  possible  to 
filter  this  off, and  even  iff  possible , presented  the  objection  of 
removing  some  of  the  mercury  with  the  other  substances.  Therefore, 
the  best  way  seemed  to  be  to  avoid  this  by  thoroughly  decomposing 
the  organic  matter  in  the  beginning, until  the  permanent  straw  color 
appeared.  The  time  for  each  decomposition  was  noted  and  recorded. 

2. CHITTENDEN  /iND  DONALDSON  METHOD. 

The  vrork  on  this  method  was  confined  to  a few  decomposi- 
tions only, since  the  nature  of  the  proceedure  suggested  great, if 
not  total  losses  of  mercury. 

Following  their  proceedure, 23  c.c.  of  pure  concentrated 
nitric  acid  is  added  to  the  blood  mexture  containing  the  mercury. 

The  mixture  contained  in  a casserole  of  OGOcc.c.  capacity  is  then 
heated  on  a hot  plate  with  occasional  stirring.  The  temperature  as 
mentioned  by  the  authors  of  this  method  is  150-160  degrees  centi- 
grade,but  v:^ith  the  blood  this  temperature  was  not  attained.  This 
would  seem  to  be  favorable.  Keeping  at  this  temperature , the  mass 
swells, thicken, and  changes  color.  At  first  a dark  brown, it  changes 
slov/ly  to  a light  yellow.  It  then  becomes  a liquid.  This  is  heated 
1 1/2  to  2 hours  until  it  takes  on  an  orange  color, or  deep  yellow 
shade.  At  this  point, the  casserole  is  removed  from  the  plate  and 
3 c.c.  of  concentrated  sulphuric  acid  added  while  stirring  vigor- 
ously. The  mixture  thickens  and  gives  off  nitrous  fumes  copiously, 
immediately  followed  by  dense  white  fumes  of  sulphur  trioxide.  ( 
The  residue  in  the  dish  is  changed  into  a black  sticky  mass  or  else 
a dry  carbonaceous  mass.  The  dish  is  again  placed  on  the  plate  and 
heated  for  a fevf  minutes.  Then  8 c.c.  of  nitric  acid  is  added, drop 


r ‘ T '' ' Vi?.' 


» t ^ ^ ■'"  ^ I * ■"  >*■  V ' , ■»  * * ' * f.  ■ ^«3 

Jh^XviR^fiSr^  ■ .ut*-  >■  ni 

^ ^ ■•  "»  ,--Kv  '.  ' -■'^  ':■  ■ yA  ^ (M 

^:i  cfl4L^^.^  ' t\j^'  »JKg>k.l -T  .‘^f  *io.^»n'r.>i-4,  t>fi4, 


^ ^ . •»  ' .'  ♦ . * ] A i-^  41 


t' , 


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*, 

.T. 


(9) 


by  drop, in  order  to  more  completely  destroy  the  organic  matter, and 
precent  the  formation  of  the  organic  sulphide.  After  this  addition, 
the  casserole  is  again  heated  for  15  minutes , after  which  the  cold 
carbonaceous  mass  is  treated  with  hot  water  in  successive  portions, 
in  order  to  extract  the  mercuric  sulphate.  This  water  is  then  evap- 
orated and  the  mercury  taken  up  from  the  residue  with  concentrated 
hydrochloric  acid.  This  extract  is  diluted  with  water  and  the  mer- 
cury sulphide  precipitated.  The  precipitate  may  then  be  dissolved 
and  titrated  as  in  the  first  method. 

In  following  out  the  above  method, the  temperatures  as 
stated  by  the  authors  exceed  those  reached  in  using  the  blood  mix- 
ture. Since  the  blood  mixture  is  more  fluid  than  solid  tissue  the 
temperature  would  naturally  be  lov/er  in  this  case.  In  extracting 
the  mercury  salt  from  the  carbonaceous  residue, the  water  was  left 
in  contact  with  the  mass  for  24  hours  in  order  to  insure  complete 
extraction.  No  difficulties  were  encountered  in  carrying  out  the 
proceedure,but  it  was  necessary  to  watch  the  mixture  very  closely 
before  adding  the  sulphuric  acid.  It  was  difficult  to  detect  the 
change  in  color  because  of  the  red  nitrous  fumes, which  were  given 
off.  It  was  necessary  to  exercise  care  in  adding  the  sulphuric  acid, 
in  order  to  prevent  any  loss  by  spattering.  Affew  drops  were  added 
at  a time  and  the  mixture  stirred  vigorously  during  addition. 

3.-W011K  ON  HARKINS  AND  SWAIN  METHOD. 

In  carrying  out  this  proceedure  500  c.c.  casseroles  were 
used  as  the  vessels,  four  determinations  were  carried  out  together. 
This  number  was  found  to  be  convenient, in  saving  time.  One  decompo- 
sition was  started  and  carried  to  the  end  of  the  first  stage.  It  i: 
was  allowed  to  heat  while  another  was  started. 


I 


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V v> 


(10) 


One  hundred  c.c.  of  concentrated  nitric  acid  was  added  to 
t?ie  blood  mixture  and  placed  on  the  hot  plate.  The  mixture  begain 
to  swell  and  required  constant  stirring  to  avoid  the  overrunning 
of  the  dish.  It  changed  color  from  a dark  brown  to  a light  yellow. 
Here  the  swelling  subsided  and  after  a little  while  became  a liquid. 
This  liquid  was  then  allowed  to  heat  for  half  an  hour,'ivhile  anotliEr 
decomposition  was  started.  The  rich  red  liquid  was  then  removed  and 
allowed  to  cool, after  which  30  c.c.  of  concentrated  sulphuric  acid 
w'as  added.  The  casserole  was  again  heated  on  the  hot  plate.  Great 
volumes  of  red  nitrous  fumes  came  off.  This  continued  for  some  time, 
when  the  liquid  begain  to  assume  a brown  color.  Here, nitric  acid 
was  added, drop  by  drop, just  enough  to  prevent  the  darkening  of  the 
liquid.  This  was  continued  until  the  thick  liquid  no  longer  chang- 
ed color.  The  mixture  was  heated  a little  longer  to  drive  off  some 
of  the  thick  white  sulphur  trioxide  fumes, in  the  meanwhile , adding 
nitric  acid  occassionally . The  casserole  was  then  removed  from  the 
heat  and  allowed  to  cool, after  which  the  residue  was  diluted  and 
reevaporated  to  a smaller  volume, in  order  to  eliminate  any  nitrous 
fiumes.  This  solution  was  then  filtered  and  the  mercury  precipitated 
from  it  in  the  usual  way, and  determined.  No  difficulty  was  encount- 
ered in  the  proceedure.  The  organic  material  was  completely  destroy- 
ed and  good  clear  solutions  were  obtained  for  the  titration.  In  rnn- 
ning  the  four  decompositions  in  the  manner  described  it  required 
the  entire  attention  of  the  writer, and  although  the  work  was  carr- 
ied out  under  the  hood  the  fumes  from  the  dishes  were  very  disagree- 
able. The  time  occuppied  \ras  about  one  hour. 

4.-  NEW  iiETHOD  TRIED. 

It  was  decided  to  modify  the  Markins -Swain  method  in 
such  a way  as  to  eliminate  the  great  losses  of  mercury  which  neces- 


'T  ■ V 


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sarily  take  place  at  the  higher  temperatures  produced  by  adding  the 
sulphuric  acid.  The  first  part  of  the  proceedure  using  the  nitric 
acid  was  carried  out  as  before, and  the  mass  reduced  to  a liquid. 

After  cooling  the  mixture  it  was  transferrdd  from  the  casserole  to 
an  800  c.c.  Kieldahl  flask  wliich  was  fitted  with  a reflux  condenser. 

The  mixture  was  then  heated  with  a bunsen  burner  to  boiling, after  | 

i 

having  added  the  sulphuric  acid, for  about  an  hour  and  one  half.  The  | 

j 

red  nitrous  fumes  were  driven  off  from  the  top  of  the  condenser,  | 

\\ 

vdiile  the  rest  of  the  material  which  volatilized  was  condensed  and  \ 
returned  to  the  flask.  Some  carbonization  was  noticeable  as  the  heat- 
ing was  continued, but  the  liquid  remained  a light  color.  The  black 
flakes  of  carbon  remained  on  top  of  the  clear  liquid.  After  most  of 
the  nitric  acid  had  been  driven  off, as  was  shown  by  the  fact  that 
scarcely  any  red  fumes  came  from  the  top  the  condenser , the  flask 
was  removed  from  the  heat  and  allowed  to  cool.  The  clear  liquid 
was  filtered  off  and  diluted.  Since  the  solution  contained  mostly 
dilute  sulphuric  acid, the  passing  in  of  hydrogen  sulphide  gave  rise 
to  a light  yellow  precipitate  of  sulphur.  This  copious  precipitate 
of  sulphur  obscured  the  precipitate  of  mercury  sulphide  for  a few 
minutes, but  it  appearred  presently  on  the  surface  of  the  solution. 
After  precipitation  was  complete  the  sulphur  and  m.ercuric  sulphide 
were  filtered  off.  The  mercuric  sulphide  was  then  dissolved  with 
nitric  and  hydrochloric  as  previously  and  titrated. 

It  was  thought  at  first  that  the  sulphur  might  interfere 
in  dissolving  the  mcrcurj''  sulphide, but  the  metal  was  easily  separ- 
ated and  the  sulphur  left  undissolved.  The  solution  finally  obtain- 
ed for  titration  gave  no  trouble, as  it  remained  clear  after  adding 
the  various  solutions  needed  for  titration.  Although  this  method 
occuppied  a little  more  time, no  disagreeable  odors  were  experienced. 


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1 


(12) 


and  it  required  less  attention.  Any  mercery  which  might  have  volatil 
izedwas  immediately  condensed  and  carried  hack  into  the  f'lask  hy 
the  water  which  was  being  returned  to  the  flask  from  the  condenser. 
Therefore, any  loss  of  mercury  caused  hy  volatilization  must  have 
occurred  in  the  first  part  of  the  process  when  the  decomposition 
was  started  with  the  nitric  acid. 

5. -METHOD  WITH  CONCENTRATED  SULPHURIC  ACID  AND  PERCHLORIC  ACID. 

It  was  decided  to  investigate  the  action  of  concentrat- 
ed sulphuric  acid  and  perchloric  acid  on  organic  tissue  in  the  hope 
that  this  might  prove  a means  of  breaking  up  the  tissue. 

Therefor  fifty  c.c.  of  concentrated  sulphuric  acid  was  add- 
ed to  the  blood  mixture  and  heated  on  the  water  bath.  A seventy  per- 
cent perchloric  acid  v»^as  obtained  and  a few  c.c.  added  at  a time, 
but  no  reaction  resulted.  The  flask  was  then  raised  to  a higher 
temperature, and  finally  to  the  boiling  point  of  the  sulphuric  acid, 
and  the  perchloric  acid  was  again  tried.  No  results  followed  and 
the  method  was  abandoned  as  unsuccessful!. 


14,^.  •;.-,-.;j.>'  ' • ‘ W ’> 


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III. RESULTS  AND  DISCUSSION 

TABLE  I 

Determinations  by  I’resenius- 

Vonl>abo  Method 

Open 

Flask 

Theor .Hg 

. Time (hr 

s)  Det.Hg. 

Hg. loss 

Hg.^  loss. 

1. 

.2316  Gr 

. 5 

.1426  Gr. 

.0890  Gr. 

38.4  1 

2. 

.3088 

4 

.2505 

.0583 

15.6  1 

3. 

.3088 

5 

.2062 

.1026 

33.2  ! 

1 

4. 

.3860 

4 

.3348 

.0512 

13.2 

5. 

.5404 

4 1/2 

.4239 

.1165 

21.2 

6. 

.6780 

3 1/2 

.4580 

.2200 

32.4 

7. 

.7540 

4 

.6326 

.1214 

16.1 

Condenser  Flask 

Theor .Hg 

Time ( hr 

s)  Det.Hg 

iig.lOSS 

lig.^  loss. 

1. 

.2316 

4 

.1174  Gr. 

.1142  Gr. 

49.3 

2. 

.3088 

3 

.2060 

.1028 

33.2 

3. 

.3088 

4 

.2013 

.1075 

34.8 

4. 

.3860 

3 

.2736 

.1124 

29.1 

5. 

.5404 

3 

.3906 

. 1498 

27.7 

6. 

.6780 

2 l/2 

.4136 

.2644 

39.0 

7. 

.7540 

3 

.6076 

.1464 

19.9 

! 

Table  I 

shows  the 

comparative 

results  of 

the  two  variations 

of 

the  Freseniu-Von  Babo 

Method.  The 

most  surprising  thing  about 

these  results 

in  the  fact 

that  the  open  flask  decomposition  gave 

the 

smallest  loss  of  mercury  in  every  single  case.  This  seems  to 

indicate  that 

the  losses 

were  not  caused  by  volatilization, to  any 

extent.  It  was 

decided  to 

investigate  the  condenser  to  determine 

i ‘I  J i<  I. 

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(14) 

if  any  volatilized  mercury  could  have  sublimed  there.  It  was  rinsed 
thoroughly  wilhh  water  and  the  washings  titrated  with  a negative  re- 
sult. The  only  way  left, then, to  explain  the  difference  in  the  losses 
from  the  same  amounts  of  mercury  under  the  two  differently  conduct- 
ed  decompositions  in  in  the  time  6f  decomposition.  The  table  shows  | 
that  the  open  flask  decomposition  required  about  an  hour  longer  in  | 

each  case, to  reach  the  right  color.  The  chlorine  will  not  break  up  | 

[ 

all  of  the  organic  material.  There  was  always  a white  mealy  residue  | 
left  in  the  bottom  of  the  flask.  This  fatty  material  resists  the  | 
action  of  the  chlorine, so  that  the  losses  in  mercury  may  correspond 
to  that  held  by  this  solid  residue.  If  this  last  fatty  material 
could  be  broken  up  by  some  other  means  and  added  to  the  recovered 
mercury, very  little  would  be  lost.  The  only  objection  here  would  be 
the  length  of  time  required  to  make  a determination. 

From  the  condenser  flask  the  mercury  losses  increase  in 
weight  as  the  amount  of  mercury  added  is  increased.  The  percentage 
of  mercury  lost  steadily  decreases  as  larger  quantities  of  mercury 
are  determined.  In  comparing  this  with  the  open  flask  figures , there 
is  a wide  variation  in  the  percent  of  mercury  lost.  However, if  the 
first  and  last  percents  are  taken, it  corresponds  very  nicely  to  the 
condenser  flask  figures.  The  mercury  losses  show  a general  increase 
as  the  quantity  of  mercury  is  increased. 

TABLE  II 

Chittenden  and  Donaldson  Method 


Theor .Hg 

Det .Hg. 

Hg. loss 

Hg.^  loss 

1. 

.3016Gr. 

.0206  Gr. 

.2810  Gr. 

93.2 

2. 

.5278 

.0186 

. 5092 

96.4 

3. 

.7540 

.0332 

.7208 

95.1 

* 


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The  extreme  accuracy  claimed,  for  this  method  by  its  authors 
is  not  verified  by  these  figures.  Almost  all  of  the  mercury  was 
lost  by  volatilization  at  the  higher  temperature  used  for  carbon- 
ization* Not  enough  determinations  were  Eun  to  ascertain  in  what 
order  the  losses  would  follow, but  the  few  in  Table  II  show  great  ( 

irregularity, depending  upon  the  variations  in  each  decomnosition,  | 

i 

The  best  thing  that  can  be  said  for  this  method  is  that  it  requires  | 
only  a short  time  to  complete  a decomposition.  | 

TABLE  III 

Harkins  and  Swain  Method 


Theor .Hg. 

Det .Hg. 

Hg. loss 

Hg.^  loss 

1. 

.2262  Gr. 

.0470  Gr. 

.1792  Gr. 

79.2 

2. 

.3770 

.0540 

.3230 

85.7 

3. 

.4524 

.0860 

.3664 

80.9 

4. 

.5278 

.1097 

.4181 

79.2 

5. 

.6036 

.0560 

.5476 

90.7 

6. 

.6786 

.0320 

. 6466 

95.2 

7. 

.7540 

.1360 

.6180 

81.9 

Av . 

84.6 

The  results  in  lable  III  show  an  average  loss  of  mercury 
to  the  extent  of  84.6  percent  of  the  theoretical.  These  results 
show  that  as  the  amount  of  mercury  determined  increases , the  J.osses 
increase  proportionately, and  the  percentage  loss  varies  from  80  to 
85  in  most  cases.  This  a much  lower  loss  than  the  (Jhittendon  and 
Donaldson  Method, but  that  was  expected  since  the  temperature  used 
here  was  not  so  high. 


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(16) 


TAiiLE  IV. 


New  Method  tried. Modified  Harkins  and  Swain 


The or .Hg. 

Det .Hg 

Hg. loss 

Hg.%  loss 

1. 

.3016  Gr. 

.0930  Gr. 

.2080  Gr. 

68.9 

2. 

.4524 

.3194 

.1330 

29.4 

3. 

.6016 

.4468 

.1548 

25.7 

It  can  he  seen  from  the  data  in  Table  IV  that  the  losses 
of  mercury  are  much  less  in  this  method  than  in  the  Harkins  and 
Swain  Method.  The  losses  increase  as  the  amount  of  mercury  added  is 
increases, while  the  percentages  of  loss  show  a gradual  decrease. 
Limited  time  permitted  only  the  three  determinations , hut  it  is 
thought  that  if  intermediate  quantities  of  mercury  were  used, the 
inteppretation  would  he  the  same  as  sho^m  hy  the  above  data.  Deter- 
mination number  one  seems  to  show  rather  too  high  percentage  loss 
in  proportion  to  numbers  two  and  three.  The  chief  objection  which 
might  be  advanced  against  this  method  is  the  length  of  time  neces- 
sary for  refluxing  the  mixture, bux,  inasmuch  as  it  requires  no  at- 
tention, the  time  is  not  really  important.  The  advantage  over  the 
Harkins  and  Swain  Method  is  that  no  disagreeable  fumes  have  to  be 
encountered.  The  chief  advantage  is  ,of  course, the  reduced  amount 
of  mercury  which  is  lost  by  volatilization.  The  sulphur  which  is 
thrown  do^m  with  the  mercury  on  precipitation  is  really  not  object- 
ionable, since  the  mercury  is  easily  dissolved  out  of  the  sulphur 


mass . 


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1171 


TABLE  V. 

Comparison  of  Methods 


Method 

Av.Theor .Hg. 

Av.Det .Hg. 

Av .Hg. loss 

Av 

l.Fresenius-Eabo 

.4576  Gr. 

.3498  Gr. 

.1084  Gr. 

24.3 

2.Chitt’n-Don' son 

.5278 

.0261 

.5017 

95.1 

3 .Harkins-Swain 

.5170 

.0744 

.4426 

84.6 

4.Nevsr  Method 

.4519 

.2864 

.1655 

41.3 

TalDle  V is  given  for  convenience  in  comparing  the  general 
results  of  the  four  methods  worked  on.  The  average  percent  loss 
gives  a pretty  fair  estimate  of  the  value  and  accuracy  of  the  meth- 
ods, except  in  the  case  of  number  four.  The  first  determination  carr- 
ied out  with  this  method  gave, for  some  reason  or  other, quite  a high 
mercury  loss.  This  result  was  too  high  to  he  consistant  with  the 
two  later  determinations  as  is  sho\m  hy  Table  IV.  As  a consequence, 
this  one  high  loss  inflates  the  average  percentage  loss  much  highrr 
than  it  really  should  be.  If  we  discard  this  one  high  loss, the  new 
n:iethod  compares  very  favorably  with  the  Iresenins-Von  Babo  I>!ethod. 

Of  course, the  averages  given  apply  to  quantities  of  mercury  bettween 
.25  to  .75  gram.  It  is  the  belief  of  the  writer  that  the  new  m.ethod 
as  described  can  be  improved  and  developed  where  m.uch  lower  losses 
of  mercury  will  occurr. 


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(18) 


IV.SUI.iJiARY  AND  CONCLUSIONS 

I.  The  four  possible  methods  for  the  toxicological  determination 
of  mercury  have  been  reviewed  and  the  three  most  promising  ones 
investigated. 

II.  Losses  of  mercury  in  the  Fresenius-Von  Babo  method  are  not  due 
to  volatilization  to  any  extent, but  to  the  undecomposed  tissue 
which  is  filtered  off  after  decomposition. 

III.  The  Chitten(?©n-Donaldson  method  uses  too  high  a temperature  for 
decomposition, thereby  volatilizing  the  greatest  percent  of  the 
mercury(95^) . 

IV.  The  Harkins -Swain  method  uses  a lower  temperature  but  the  decom- 

p position  temperature  is  high  enough  to  allow  great  losses  of  mer- 
cury. This  makes  it  unsuitable  for  determination  of  small  quan- 
tities of  mercury 

V.  Disagreeable  fumes  are  encountered  in  this  method. 

VI.  The  new  method  tried  gave  much  smaller  mercury  losses  than  either 
the  Ciiittenden-Donaldson  or  Harkins-Swain  methods. 

VII.  The  new  method  compares  very  favorably  with  the  Fresenius-Von 
Babo  method 

VIII.  It  can  be  developed  so  as  to  give  much  lower  losses. 

IX.  Of  the  four  known  methods  Fresenius-Von  Babo  method  gives  the 
smallest  losses, and  seems  to  be  the  most  suitable  for  determin- 
ing small  quantities  of  mercury  in  organic  tissue.lt  is  better 
because  it 

1. Uses  a comparatively  low  temperature. 

2.  Gives  no  disagreeable  odors. 

3.  Uses  only  one  acid. 


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V.  BIBLIOGRAPHY 

1.  Bulletin  de  la  Societe  chimique  24,250.  1875 

2.  Traite  de  Toxicologie  1,494.  1852 

3.  Filhol-  Thesis  Paris  1848 

4.  American  Chemical  Journal  Vol.II  No. 4.  1880 

5.  Berichte  54B  pp.2079  -1921 

6.  Journal  American  ChemicJil  Society  30,928 

7.  Treadwell-Hall  Vol.II  pp.720  1918 

8.  Annalen  der  chemie  und  Pharmazie  49,306-  1844 


